Detergent composition and method of making same



Patented June 10, 1941 DETERGENT COMPOSITION AND METHOD OF MAKING SAME Waldemar 0. Mitscherling, Flushing, N. Y., as-

signor to John J. O'Connor, New York, N. Y.

No Drawing. Application October 3, 1940, 'Serial N0. 359,545

2 Claims.

The present invention is directed to the production of new addition and hydrolysis products, and more particularly to those adapted for use as detergents or the like.

It ls among the objects of my invention to form a new and improved chemical substance or substances which shall have highly useful properties as a detergent and emulsifying agent.-

Another object of my invention is to produce a series of compounds of the water dispersible type, of the class sometimes referred to as hyurotropic fats.

The present invention is based upon my discovery that a monobasic carboxylic acid, such as for instance oleic acid, and particularly the higher fatty acids of this type, may be combined with more than one molecule of an alkylolamine, to form addition products which after further treatment may be dispersed in water. These possess many useful properties in either neutral, alkaline or acid media. The resultant substances are readily soluble in water and will retain their effectiveness in the presence of either calcium or magnesium salts.

In forming these products the addition may take place at temperatures below 100 C. Operations have been successfully carried out as low as 30 C. It may be stated that the temperature'range as previously practiced in making products of this general type has been above 100 C., and as high as 250 C. It may be also stated that side reactions, at higher temperature, take place, which cause decomposition of the resulting product. I have found that for practical purposes the best temperatures used in my process are between 60 C. and 80 C.

The addition may be made in neutral solutions or with the aid of a suitable agent, either of an alkaline or acid character, but no metallic hydroxides or salts usually designated as soap are used in my process. The presence of the agent has an effect upon the speed of the reaction and the temperature required. I have used various agents and I also have found that excellent products are created without the use of an agent.

Substances having chemical properties of the type of monobasic carboxylic acids and the like, including low molecular weight monocarboxylic acids such as the lower" fatty acids and other similar acids having up to six carbon atoms in the molecule are suitable for my purpose. However, I prefer the aliphatic monocarboxylic acids having at least six carbon atoms and more, particularly those containing from 12 to 18 carbon atoms. The addition products prepared by the use of the latter mentioned acids of higher molec cular weight are clearly differentiated in their properties and uses, being superior to products made with acids of lower molecular weight. It will be understood that wherever I use the term higher molecular weight" aliphatic monocarboxylic acids, or the term higher fatty acids, I intend to cover such acids having a chain of at least six carbon atoms.

Included in the acids mentioned above which are suitable, are those derived from naturally occurring vegetable glycerides, oils and fats, hydrogenated or unhydrogenated. Unhydrogenated products yield transparent solutions, while hydrogenated products yield opaque or solid products. Included in my invention are oils of animal and vegetable origin which are giycerides of the higher fatty acids. Examples of suitable fatty acids are: stearic acid, palmitic acid, oleic acid, linoleic acid, lauric acid, myristic acid, cocoanut oil fatty acids, ricinoleic acid, and others, such as the wax and fatty wax acids. In place of the fatty acids, I may also employ acid anhydrides. In general, any organic derivative containing the C=O group may be used.

I include in the term alkylolamine in describing the invention in a general sense, substances like monoethanolamine, diethanolamine, triethanolamine, dialkylalkylolamines, diethylethanolamine, or monoethylalkylolamines, butanolamine, pentanolamine, hexanolamine, cyclohex- 'ylethanolamine, isobutanolamine, N-phenyl ethanolamine, laurylolamine, triethanolammoniumhydroxide, and aryl and cycloalkylalkylolamines.

After addition of the amine and acid have taken place at least in part, the addition product is subjected to hydrolysis. To accomplish this, a sufficient amount of water is added to the product, preferably with stirring, the spontaneous rise of temperature causing hydrolysis to begin and continue. As the result of the hydrolysis, free hydroxy groups have been introduced into the addition product making the same valuable as a detergent and as an emulsifying agent.

As a specific example of the operation of my process, 1 gallon of triethanolamine is placed into an agitating tank and without external heating, one-fifth of a gallon of oleic acid is gradually added with stirring. The mixture increases in viscosity and agitation is continued for about 10 minutes, during which time spontaneous heating takes place, indicating that a reaction of the addition type has occured. When the temperature begins to fall, an additional one-fifth of a gallon 01 oleic acid is slowly added during agitation. Again a rise in temperature will occur, this time the rise being from 10-15" C. higher than in the first stage. The syrupy appearance of the product is maintained. After the temperature again begins to drop, showing that the reaction is complete, an additional threefifths of a gallon of oleic acid are added slowly, with stirring, as set forth above.

There is then added to the product a mixture of one-fifth of a gallon of water and an equal amount of monoethyl ether of diethylene glycol, and the stirring is continued The temperature again begins to rise and the viscosity is reduced. Usually, the rise'in temperature is about 20 C. After the reaction is complete, four-fifths of a gallon of monoethyl ether of diethylene glycol and 10.8 gallons of water are added and the agitation continued to complete the hydrolysis. During all stages of the reaction, the temperature does not reach 100 C., and usually the temperature does not rise higher than 80 C.

The addition of a glycol ether to the water in the latter stage of the operation is quite essen-' tial, as it acts to catalyze the hydrolysis of the amino, groups and at the same time prevents a saponiilcation reaction and also prevents decomposition of the initial addition product.

Much of the water added in the hydrolysis is chemically combined and it has been found that approximately 3.7 parts by weight of water are so combined that they cannot be removed by distillation. The final product of the hydrolysis is liquid even though no excess of water is present over that necessary to cause the hydrolysis.

When small quantities ofthe ingredients are reacted, continual heating must be supplied from an outside source. However, when larger quantities are used the exothermic reaction creates sufiicient heat to promote the reaction smoothly and completely. I do not exactly limit my invention to products resulting from the combination of the mixtures of alkylolamines and higher fatty acids. The molecular ratio of the former to the latter may be over two to one and even up to eight to one in some cases. I also include within the scope of my invention, the reaction to form addition products of substances which contain a substantial proportion of substitution 1 products of alkylolamines. 7

According to the present process, decomposiand is the approximate proportion necessary to effectively react with the initial addition product and particularly with the amino groups; The alkyloamine itseli can be of the mono-, di-, or tritype, for instance, monoethanolarnine, or diethanolamine, or triethanolamine. These a1- kylolamines exhibit an alkaline character with a pH value of 8.3. The hydrolysis immediately increases the alkalinity toabout 9.2, thus acting similarly. to an inorganic hydroxy or basic salt. However, the reaction involving the water cannot be called a saponification. The addition of a glycol ether, such for instance as diethylene glycol monoether as a solvent, causes in this particular product greater solubility for fats, materially improving the product. The amount of the addition of the glycol ether is not critical; it depends entirely on the type product one wishes to produce. tion of one to three parts by volume of the glycol ether to the above-described hydrolyzed addition product will produce. an excellent composition which can be diluted with water in any proportions.

What I claim is:

1. A method of making detergent compositions which consists essentially in providing an alkylolamine, adding oleic acid thereto with stirring, the temperature being approximately room temperature, the ratio of acid to amine being about 1 to 5 by volume, allowing an addition reaction to take place until the spontaneous rise in temperature resulting from said reaction ceases, adding a further amount of said acid and repeating the procedure until volume of acid equals that of said amine, adding with stirring an amount of water equal to about 5 5 part by volume to the product of said amine and acid together with /5 part by volume, as a catalyst, of monoethyl ether of diethylene glycol, allowing hydrolysis to take place with a spontaneous rise in temperature, adding about 10.8 parts by volume oi water and 3 part by volume of said ether and allowing the hydrolysis to go to completion, whereby a composition containing products of hydrolysis, monoetflhiyl ether of diethylene glycol and water res s.

2. A method of making detergent compositions which consists essentially in providing an alkyloltion, which occurred in the prior art high temperature processes, cannot take place because the mixture of ingredients, which has been described above, is kept at a low temperature, and during the reaction, water is added for the purpose, not of diluting the compound, but forming immediately the respective new hydrolyzed compounds which are desirable in my product. I also include within the scope of my invention, solutions in suitable solvents of products which contain substantial proportions of addition products of the alkylolamines with higher fatty acids, or the like.

In my particular case the alkylolamine addition products, which are formed in the first stage of the process, are hydrolyzed in water in ratio by volume of 1 part product to 3.7 parts of water. This ratio is not an arbitrary figure, but a scientific calculation based on experimental evidence amine, adding thereto with stirring a higher fatty acid derived from vegetable and animal glyceride oils, the temperature being approximately room temperature, the ratio of acid to amine being about 1 to 5 by volume, allowing an addition'reaction to take place until the spontaneous rise in temperature resulting from said reaction ceases, adding a further amount of saidacid and repeating the procedure until volume of acid equals that of said amine, adding with stirring an amount of water equal to about t part by volume to the product of said amine and acid together with part by volume, as a catalyst, of monoethyl ether of diethylene glycol, allowing hydrolysis to take place with a, spontaneous rise in temperature, adding about 10.8 partsby volume of water and /5 part by volume of said ether and allowing the hydrolysis to go to completicn, whereby a composition containing products of hydrolysis, said glycol ether and water results. WALDEMAR O. MITSCHERLING.

However, I have found that the addi- 

